Dyeing preparation and its conversion to dyestuffs



Patented Aug. 7, 1934 .UNITED STATES DYEING PREPARATION AND ITS CONVER- SION T DYESTUFFS Arthur Zitscher, Wilhelm Seidenfaden, and Karl Jellinek, Oifenbach-on-the-Main, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation 0! Delaware No Drawing. Original application January 5,

1932, Serial No. 584,900. Divided and this application February 4, 1933, Serial No. 655,250. In Germany January 13, 1931 14 Claims.

Our present invention relates to dyeing preparations and their conversion to dyestuffs.

This application is a divisional application of our U. S. Patent No. 1,932,152,.

6 These dyeing preparations contain a hydrazine-sulfonate of the diarylamine series, corresponding to the probable general formula:

XNH-RNH NH SO: alkali metal wherein X means a naphthalene nucleus or a rad- I0 ical of the benzene series which may contain in the para-position to the NH-group a further -NHNHSOaalkali-metal group and R means a radical of the benzene series, and a combining component containing a hydroxy or 15 an O-alkali-metal group whereof the adjacent position is capable of attaching an aryl-azo group.

As combining components of the aforesaid kind may be named: 2-hydroxynaphthalene, its nuclear substitution products as, for instance, aroylamino-hydroxynaphthalenes, (2-hydroxy-naphthalene-3 -carbonyl) -amino-aryls (as described in U. S. Patents No.. 1,101,111 and No. 1,140,747), (6halogen-or G-arylamino-2-hydroxy-naphthalene-3-carbonyl-amino-aryls (see German Patent No. 396,519 and British Patent No. 330,349), derivatives of 1-hydroxy-naphthalene-4-carbo1;ylic acid (see U. S. Patent No. 1,453,660), as, for instance, l-hydroxy-naphthalene-4-phenyl-ketone; compounds containing an acidic methylene group capable of being combined with diazo-compounds, as, forinstance, pyrazolones and derivatives of p-ketonaldehyde, for instance, acetoacetyl-amino-aryls and di- (aceto-acetyl-amino) aryls (see U. S. Patents No. 1,594,864, No. 1,594,866, No. 1,594,867, No. 1,580,709, No. 1,634,090), dihydroxy-quinolines (see U. S. Patents No. 1,820,039, No. 1,846,073 and No. 1,846,074, British Patent No. 332,940), (2-hydroxy-carbazole-3-carbonyl) -amino-aryls,. (2-hydroxy-benzo-carbazole 3 carbonyl) -amino-aryls, (2-hydroxy-anthracene-3-carbonyl) -an iino-aryls.

These dyeing preparations yield, when applied in an alkaline medium to fibers, by steaming 15 only, insoluble azo-dvestuffs on the fibers.

'Such applying to the fibers consists in dyeing according to the one-bath-method or in printing. The dyebath or the printing paste or also the powderous dyeing preparations themselves 30 are advantageously mixed with dyeing assiste ants having wetting, emulsifying or solvent prop erties, or also with the additional agents customary in using nitrosamine-printing colors, as, for instance, chromate. Furthermore, sulfur is 6 advantageously added to the printing paste.

Thereby, in some cases, the quickness and the evenness of the dyestufl formation is favorably influenced.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in Centigrade degrees; but we wish it, however, to be understood that we are not limited to the particular conditions or specific products mentioned therein.

(1) 130 parts of the sodium salt of 3-methoxy- 65 diphenylamine-4 hydrazinesulfonic acid of 85.4% strength, 100 parts of 1-(2'-hydrom-naphthalene-3 '-carbonyl-amino) -3-nitrobenzene and 30 parts of ground caustic soda are triturated together to form a homogeneous powder. 260 parts of dyestufi? preparation are thus obtained.

(2) 15.75 parts of the sodium salt of dlphenylamine-4-hydrazine-sulfonic acid of 48% strength, 8.5 parts-of the disodium salt of 1-(2'-hydroiwnaphthalene 3' carbonyl-amino) -naphthalene and 6.75 parts of anhydrous sodium acetate are triturated until a homogeneous powder isformed. In this manner, 31 parts of dyestufl preparation are obtained. v

(3) 80 parts of 1-(2'-hydroxy-naphthalene-3- carbonyl-amino)-2-methoxy-benzene, 94.8 parts of the sodium salt of diphenylamine-4.4'-dihydrazine-sulfonic acid of 72.3% strength and 25.2 parts of anhydrous sodium acetate are ground to form a homogeneous powder. 200 parts of dye- 85 stuff preparation are thus obtained; j

A printing paste which contains 50 parts of the above described dyestuff preparation, 20 parts of thiodiglycol, 20 parts of caustic soda lye of 34 B., 7 parts of flowers of sulfur, 20' parts of neutral sodium-chromate solution 1:4, 393 parts of water and 500 parts of starch tragacanththickening, is printed on thematerial, which is dried, steamed for 5 minutes in the Mather- Piatt, rinsed while hot, soaped and rinsed again.

In this manner, a bluish-black print is obtained. 7

(4) 137.2 parts of the sodium salt of 4-methoxy-diphenylamine-4-hydrazine-sulfonic acid of 95.8% strength, 24 parts of anhydrous sodium sulfite and 33.6 parts of flowers of sulfur are ground intimately, then 105.2 parts of (2-hydroxy-naphthalene-3-carbonyl-ainino) benzene are added to the mixture and the whole is around 105 to form a homogeneous powder. 300 parts of a powdery preparation are thus obtained.

A printing paste, containing 42 parts 'of the above mixture, 20 parts of thiodiglycol, 15 path of caustic soda lye of 34 B., 20 parts of sodium- 110 chromate solution 1:4, 403 parts of water and 500 parts of starch tragacanth-thickening, is printed, the goods are dried, steamed for 5 minutes in the Mather-Flatt, rinsed while hot, soaped and rinsed again.

In this manner, a clear blue print is obtained.

(5) 60 parts of (2'-hydroxy-naphthalene-3'- carbonyl-amino) -benzene, 9 parts of 4.4'-bisaceto acetylamino 3.3-dimethyl-diphenyl, 144 parts of the sodium salt of 4-methoxy-diphenylamine-4-hydrazine-sulfonic acid of 59.9% strength and 45 parts of anhydrous sodium acetate are ground to form a homogeneous powder. In this manner, 258.8 parts of dyestufl preparation are obtained.

A printing paste which contains 86 parts of the foregoing mixture, 20 parts of thiodiglycol, 20 parts of caustic soda lye of 34 B., 20 parts of sodium-chromate solution 1:4, 354 parts of water and 500 parts of starch tragacanth-thickening, is printed on the material which is aftertreated as described in Example 3.

A black print is thus obtained.

(6) 157.5 parts of the sodium salt of 3-methyl- 4' methoxy-diphenylamine 4 hydrazine sulffonic acid of 33% strength are ground intimately with 60 parts of anhydrous sodium acetate. To this mixture, there are added 6 parts of flowers of sulfur and 45 parts of 1-(2'-hydroxy-naphthalene-3'-carbonyl-amino) 2 methoxy benzene and the whole is ground to form a homogeneous powder. 268.5 parts of dyestuff preparation are thus obtained.

A printing paste, containing 89.5 parts of the above described dyestuif preparation, 20 parts of caustic soda lye of 34 B., 20 parts of thiodiglycol, 20 parts of sodium-chromate-solution 1:4, 350.5 parts of water and 500 parts of starch tragacanth-thickening, is printed on the goods which are treated as described in Example 3.

In this manner, a navy blue print is obtained.

('1) 157.5 parts of well pressed sodium salt of diphenyl-amine-4-hydrazine-sulfonic acid of 48% strength are ground intimately with 67.5 parts of anhydrous sodium acetate; then 75 parts-of 1(2'-hydroxy-naphthalene-3'-carbonyl amino) 3-nitrobenzene are added and the mixture is ground to form a homogeneous powder. In this manner, 300 parts of a powdery product are ob tained.

A printing paste which contains 60 parts of the above described powder, 20 parts of thiodiglycol, 15 parts of caustic soda lye of 34 B., 385 parts of water, 500 parts of starch tragacanth-thickening and 20 parts of neutral chromate solution 1:4, is printed on the material which is after-treated as described in Example 3.

A dark blue print is thus obtained.

(8) 31.5 parts of the moist sodium salt of 2' methoxy-diphenylamine 4 hydrazine sulfonic acid of 63% strength are ground with 12 parts of anhydrous sodium acetate: To this mixture, there are added 2 parts of precipitated sulfur and 15 parts of 1-(2'-hydroxy-naphthalene-3'- carbonyl-amino) -4-chloro-benzene and ground to form a homogeneous powder. 60 parts of dyestuff preparation are thus obtained.

A printing paste, containing 60 parts of this preparation, 20 parts of caustic soda lye of 34 B., 20 parts of thiodiglycol, 20 parts of neutral chromate solution 1:4, 380 parts of water and 500 parts of starch tragacanth-thickening, is printed on the goods which are treated as described in Example 3.

In this manner, a reddish-blue print is obtained: n

(9) A printing paste which contains 20 parts of (2' hydroxy-naphthalene-3'-carbonyl-amino)- benzene, parts of the sodium salt of diphenylamine-4.4-dihydrazine-sulfonic acid of 21.5% strength, 20 parts ofv thiodigylcol, 20 parts of caustic soda lye of 34 B., 20 parts of sodium-chromate solution 1:4, 7 parts of finely powdered sulfur, 333 parts of water and 500 parts of starch tragacanth-thickening, is printed on the material which, thereupon, is dried, steamed for 5 minutes in the Mather Platt, rinsed while hot, soaped and rinsed again.

In this manner, a bluish-black print is ob tained.

(10) A printing paste which contains 15 parts of 1-(2-hydroxy-anthracene-3' carbonyl amino) -2-methyl-benzene, 28.5 parts of the sodium salt of diphenylamine-4-hydrazine-sulfonic acid of 48% strength, 20 parts of thiodiglycol, 15 parts of caustic soda lye of 34 B., 401.5 parts of water, 500 parts of starch tragacanth-thickening and 20 parts of neutral chromate solution 1:4, is printed on the goods which are after-treated as described in Example 3.

In this manner, a bluish-green print is obtained.

(11) A printing paste which contains 15 parts of 1 (2'-hydroxy-naphthalene-3'-carbonyl-amino) -2-methoxy-benzene, 305 parts of the sodium salt of 3-(phenyl-su1fonyl) -diphenylamine- 4-hydrazine-sulfonic acid of 78.9% strength, 20 parts of thiodiglycol, 15 parts of caustic soda lye of 34 B., 399.5 parts of water, 500 parts of starch tragacanth-thickening and 20 parts of neutral chromate solution 1:4, is printed on the material which is after-treated as described in Example 3.

A blue print is thus obtained.

(12) Bleached calico fabric is impregnated with a solution, containing 15 parts of 1-(2'-hydroxy-naphthalene-3'-carbonyl-amino) -4 chloro-benzene, 23 parts of the sodium salt of 4'- methoxy diphenylamine 4 hydrazine-sulfonic acid of 59.9% strength, 20 parts of caustic soda lye of 34 B., 20 parts of thiodiglycol, 20 parts of sodium chromate solution 1:4, 50 parts of tragacanth mucilage 65:1000 and 852 parts of water.

Thereupon, the goods are dried, steamed for 5 minutes in the Mather-Flatt, rinsed and soaped.

In this manner, a blue self-dyeing is obtained.

All the dyestuffs described in the table of U. S. Patent No. 1,920,542 may also be produced on the material according to our present invention if the diazo-sulfonates mentioned in the said table are replaced by the corresponding hydrazine sulfonates of the present application.

Since an object of the present invention is to prepare dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the .appended claims contain no substituents as are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestufis to alkalles. Substitu cuts of this kind are the suifonic acid, the carboxylic acid and the hydroxy group.

We claim:

1. The dyeing preparations comprising a hydrazine-sulfonate of the diaryl-amine series corresponding to the probable general formula: X-NHRNHNH-S0:alkali-metal wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in or an O-alkali-metal group whereof the adjacent position is capable of attaching an aryl-azo group, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

2. The dyeing preparations comprising a hydrazine-sulfonate of the diaryl-amine series corresponding to the probable general formula: XNHRNHNH-SOaalka1i-metal wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in the para-position to the NH-group a further-NH- NH-SO:--alkali-metal group and R means a radical of the benzene series, and a combining component of the formula:

wherein R represents a radical of the naphthalene, anthracene or carbazole series and Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

3. The dyeing preparations comprising a hydrazine sulfonate of the diarylamine series corresponding to the probable general formula:

wherein X means a naphthalene nulceus or a radical of the benzene series which may contain in the para-position to the NH-group a further NH-NHSOaalkali-metal group and R means a radical of the benzene series, and a (Z-hydroxynaphthalene- 3 -carbonyl-amino) -aryl of the formula:

wherein Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

4. The dyeing preparations comprising a hydrazine-sulfonate of the diphenylamine series corresponding to the probable general formula:

YONHONHNHSO;alkali-metal wherein the benzene nuclei may contain alkyl, alkoxy, aryloxy, halogen or nitro substituents and Y means hydrogen or one of the aforesaid substituents or a second NHNHSOa-alkalimetal group, and a (2-hydroxy-naphthalene-3- carbonyl-amino) -aryl of the probable formula:

on v

CONHZ wherein'Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestufis insoluble in water and alkali.

5. The dyeing preparation comprising the sodium salt of diphenylamine-4.4'-dihydrazinesulfonic acid and 1-(2'-hydroxy-naphthalene-3'- carbonyl-amino) 2 methoxy benzene, which dyeing preparation yields, when brought onto fibers, by steaming bluish-black dyeings and printings.

6. The dyeing preparation comprising the sodium salt of 4'-methoxy-diphenyl-amine-i-hydrazine-sulfonic acid and (2-hydroxy-naphthalene-3'-carbonyl-amino)-benzene, which dyeing preparation yields, when brought onto fibers, by steaming clear blue dyeings and printings.

7. The dyeing preparation comprising the sodium salt of 4-methoxy-diphenylamine-4- hydrazine-sulfonic acid, (2-hydroxy-naphthalene-3'-carbonyl-amino)-benzene and 4.4'-bisaceto acetyl amino 3.3 dimethyl diphenyl, which dyeing preparation yields, when brought onto fibers, by steaming black dyeings and printings.

8. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 1, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

9. A'process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 2, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

10. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 3, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

11. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 4, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

12. A process which comprises applying to vegetable fibers the dyeing preparation claimed in claim 5, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

13. A process which comprises applying to vegetable fibers the dyeing preparation claimed in claim 6, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

14. A process which comprises applying to vegetable fibers the dyeing preparation claimed in claim 7, drying the fibers thus applied, to steaming and finishing by rinsing and soaping.

ARTHUR ZITSCHER. WILHELM SEIDENFADEN. KARL JELLINEK. 

